JPH0251217B2 - - Google Patents
Info
- Publication number
- JPH0251217B2 JPH0251217B2 JP56037834A JP3783481A JPH0251217B2 JP H0251217 B2 JPH0251217 B2 JP H0251217B2 JP 56037834 A JP56037834 A JP 56037834A JP 3783481 A JP3783481 A JP 3783481A JP H0251217 B2 JPH0251217 B2 JP H0251217B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- fes
- organic solvent
- active material
- batteries
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000011149 active material Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims 1
- 229910000339 iron disulfide Inorganic materials 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- WMVRXDZNYVJBAH-UHFFFAOYSA-N dioxoiron Chemical compound O=[Fe]=O WMVRXDZNYVJBAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明は有機溶媒電池の放電特性を向上せしめ
る正極、更に詳しくはその活物質に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive electrode that improves the discharge characteristics of an organic solvent battery, and more particularly to an active material thereof.
負極活物質としてリチウム、ナトリウム等の軽
金属を用いた有機溶媒電池は、エネルギー密度が
高く、広い温度領域で使用することができ、また
その貯蔵特性もすぐれるなどの理由によつて、電
卓、時計、メモリのバツアツプ電源として汎用さ
れている。 Organic solvent batteries that use light metals such as lithium and sodium as negative electrode active materials have high energy density, can be used in a wide temperature range, and have excellent storage properties, so they are used in calculators and watches. It is widely used as a memory backup power supply.
この有機溶媒電池の発電要素は、負極、電解
液、正極から構成される。一般に、負極として
は、リチウム、ナトリウムなどの軽金属が用いら
れ、また電解液としては、プロピレンカーボネー
ト、γ−ブチロラクトン、ジメトキシエタンなど
の有機溶媒中に、過塩素酸リチウム、ホウフツ化
リチウムなどの電解質を溶解して成る溶液が用い
られる。 The power generation element of this organic solvent battery is composed of a negative electrode, an electrolyte, and a positive electrode. Generally, a light metal such as lithium or sodium is used as the negative electrode, and an electrolyte such as lithium perchlorate or lithium borofluoride is used in an organic solvent such as propylene carbonate, γ-butyrolactone, or dimethoxyethane. A solution obtained by dissolving it is used.
この有機溶媒電池において、その正極活物質と
しては3V系では二酸化マンガン（MnO2）、フツ
化炭素［（CFx）ｎ］、また1.5V系では酸化ビス
マス（Bi2o3）、酸化銅（CuO）、硫化鉄（FeS）、
二酸化鉄（FeS2）が知られている。 In this organic solvent battery, the positive electrode active materials are manganese dioxide (MnO 2 ) and carbon fluoride [(CFx)n] in the 3V system, and bismuth oxide (Bi 2 o 3 ) and copper oxide (CuO 2 ) in the 1.5V system. ), iron sulfide (FeS),
Iron dioxide (FeS 2 ) is known.
一方、1.5V系電池として酸化銀電池が小型機
器に広く用いられているが、近年、銀の価格が高
騰し、該酸化銀電池が価格上昇している。そのた
め、放電特性にすぐれかつ安価な1.5V系有機溶
媒電池の開発が強く求められている。 On the other hand, silver oxide batteries are widely used as 1.5V batteries in small devices, but in recent years, the price of silver has soared, and the price of silver oxide batteries has increased. Therefore, there is a strong demand for the development of an inexpensive 1.5V organic solvent battery with excellent discharge characteristics.
さて、上記した正極活物質を含む正極を用いた
有機溶媒電池のうち、正極活物質CuO、FeSのも
のは、その放電電圧が1.2〜1.4Vと低く、また
Bi2O3のものは高価となる。そのため、FeS2を用
いた有機溶媒電池が注目を集めている。 Now, among organic solvent batteries using positive electrodes containing the above-mentioned positive electrode active materials, those with positive electrode active materials such as CuO and FeS have a low discharge voltage of 1.2 to 1.4V, and
Bi 2 O 3 products are expensive. Therefore, organic solvent batteries using FeS2 are attracting attention.
正極活物質にFeS2を用いた有機溶媒電池は既
に知られている（特開昭47−16928号）。 An organic solvent battery using FeS 2 as a positive electrode active material is already known (Japanese Patent Application Laid-open No. 16928/1983).
しかしながら、この電池は放電の進行ととも
に、放電電圧が２段階に変化して、放電平坦性に
劣る。また、正極活物質がFeSの電池は、放電電
圧が２段に変化することはないが、上記したよう
にその放電電圧は低くかつ容量密度もFeS2を正
極活物質として用いた電池よりも小さい。 However, in this battery, the discharge voltage changes in two stages as the discharge progresses, and the discharge flatness is poor. In addition, batteries with FeS as the positive electrode active material do not have a two-step change in discharge voltage, but as mentioned above, the discharge voltage is lower and the capacity density is lower than that of batteries with FeS 2 as the positive electrode active material. .
本発明者らは、正極活物質としてFeS2を含む
正極の上記のような欠点を解消するために鋭意研
究を重ねた結果、FeS2を予め不活性ガス中で所
定温度に加熱処理してから活物質として用いる
と、得られた有機溶媒電池の放電平坦性が改善さ
れ、かつ容量密度もFeSの場合に比べて大きくな
るという事実を見出し、本発明を完成するに到つ
た。 The inventors of the present invention have conducted extensive research to eliminate the above-mentioned drawbacks of positive electrodes containing FeS 2 as a positive electrode active material. The present invention was completed based on the discovery that when used as an active material, the discharge flatness of the obtained organic solvent battery is improved and the capacity density is also increased compared to the case of FeS.
本発明は、放電平坦性にすぐれかつ容量密度も
大きい有機溶媒電池に用いて有効な正極、とくに
その正極活物質を提供することに目的がある。 An object of the present invention is to provide a positive electrode, particularly a positive electrode active material thereof, which is effective for use in an organic solvent battery with excellent discharge flatness and high capacity density.
すなわち、本発明の正極は、活物質が不活性ガ
ス雰囲気中で400〜600℃に加熱処理されたFeS2
を含むことを特徴とする。 That is, in the positive electrode of the present invention, the active material is FeS 2 heat-treated at 400 to 600°C in an inert gas atmosphere.
It is characterized by including.
本発明にかかる正極活物質は、従来から活物質
として用いられているFeS2の粉末を不活性ガス
雰囲気中で加熱処理して得ることができるが、そ
の他FeS2とCuO、Cu2SあるいはBi2O3との混合
物を同様に処理して得ることもできる。不活性ガ
ス雰囲気としては窒素、アルゴン、ヘリウムの単
独又はこれらの混合ガスのいずれでも良い。 The positive electrode active material according to the present invention can be obtained by heat-treating FeS 2 powder, which has been conventionally used as an active material, in an inert gas atmosphere. A mixture with 2 O 3 can also be obtained by similar treatment. The inert gas atmosphere may be nitrogen, argon, helium, or a mixture thereof.
加熱処理温度は、400〜600℃の範囲に設定され
る。該温度が400℃未満の場合には、効果があら
われず、また600℃を越えるとFeS2の殆どが熱分
解してFeSに変化し、放電平坦性は改善されるが
その容量密度棒は小さくなり不都合である。 The heat treatment temperature is set in the range of 400 to 600°C. If the temperature is less than 400℃, no effect will appear, and if it exceeds 600℃, most of FeS 2 will thermally decompose and change to FeS, improving the discharge flatness, but the capacity density bar will be small. This is inconvenient.
本発明の正極は、上記のようにして得られた活
物質を、常用の導電材と結着材に混合した後、成
形することによつて容易に作製することができ
る。 The positive electrode of the present invention can be easily produced by mixing the active material obtained as described above with a commonly used conductive material and a binder, and then molding the mixture.
以下に本発明を、第１図に示した有機溶媒池に
則して、更に詳しく説明する。 The present invention will be explained in more detail below with reference to the organic solvent pond shown in FIG.
実施例
FeS2の粉末を窒素気流中で、300℃、400℃、
500℃、600℃、650℃の各温度で４時間加熱処理
して得られた５種類の試料粉末及びFeS粉末の計
６種類の粉末を用意した。Example FeS 2 powder was heated at 300℃, 400℃ in a nitrogen stream,
A total of six types of powder were prepared, including five types of sample powders obtained by heat treatment at temperatures of 500°C, 600°C, and 650°C for 4 hours and FeS powder.
これら６種類の試料粉末が90.6重量％、黒鉛粉
末が7.4重量％、ポリテトラフロロエチレン粉末
が2.0重量％の配合比となるようにそれぞれの粉
末を秤量して配合した後、Ｖミキサーで混合し
た。得られた混合粉末を常法により成形して、直
径15mm厚み0.4mmの正極ペレツト６種類を作成し
た。300℃加熱処理したFeS2を有する正極を試料
１、400℃加熱処理したFeS2を有する正極を試料
２、500℃加熱処理したFeS2を有する正極を試料
３、600℃加熱処理したFeS2を有する正極を試料
４、650℃加熱処理したFeS2を有する正極を試料
５、FeSを有する正極を試料６とした。 These six types of sample powders were weighed and blended so that the blending ratio was 90.6% by weight, graphite powder 7.4% by weight, and polytetrafluoroethylene powder 2.0% by weight, and then mixed using a V-mixer. . The obtained mixed powder was molded by a conventional method to prepare six types of positive electrode pellets each having a diameter of 15 mm and a thickness of 0.4 mm. Sample 1 is a positive electrode with FeS 2 heat-treated at 300°C, Sample 2 is a positive electrode with FeS 2 heat-treated at 400°C, Sample 3 is a positive electrode with FeS 2 heat-treated at 500°C, and Sample 3 is a positive electrode with FeS 2 heat-treated at 600°C. Sample 4 was a positive electrode containing FeS 2 heat-treated at 650°C, Sample 5 was a positive electrode containing FeS, and Sample 6 was a positive electrode containing FeS.
次に、第１図に示すように、各正極１と金属リ
チウム円板２（負極）を、1M過塩素酸リチウム
を溶解するプロピレンカーボネート及び１、２−
ジメトキシエタンとから成る混合電解液を含浸保
持したセパレータ３を介して当接させ、これらを
ステンレススチール製のケース４に収納した後、
ケース４には、負極端子も兼ねる板５（負極封口
板）を端部周縁に設けたガスケツト６を介して冠
着し、更にケース４の開口端を内側方向に折り曲
げて封口して、直径20mm総高1.6mmの有機溶媒電
池を組立てた。 Next, as shown in FIG.
After being brought into contact with each other through a separator 3 impregnated with a mixed electrolyte consisting of dimethoxyethane and housed in a stainless steel case 4,
A plate 5 (negative electrode sealing plate) that also serves as a negative electrode terminal is attached to the case 4 via a gasket 6 provided around the edge of the end, and the open end of the case 4 is further bent inward and sealed to form a 20 mm diameter plate. An organic solvent battery with a total height of 1.6 mm was assembled.
なお、これら電池の組立ては、いずれも相対湿
度４％以下の乾燥雰囲気中で行なつた。 Note that these batteries were all assembled in a dry atmosphere with a relative humidity of 4% or less.
これら６種類の有機溶媒電池に6.5kΩの負荷を
接続し、常温で定負荷放電を行なつた。それぞれ
の電池の放電特性の結果を第２図に示した。 A load of 6.5 kΩ was connected to these six types of organic solvent batteries, and constant load discharge was performed at room temperature. The results of the discharge characteristics of each battery are shown in FIG.
第２図から明らかなように、本発明の正極（試
料２、３、４）を用いた電池は、試料１の正極を
用いた電池に比べ放電平坦性にすぐれており、ま
た試料５、試料６の正極を用いた電池に比べてそ
の放電持続時間が長く、容量密度の大きいことが
判明した。 As is clear from FIG. 2, the batteries using the positive electrodes of the present invention (Samples 2, 3, and 4) have superior discharge flatness compared to the batteries using the positive electrode of Sample 1. It was found that the discharge duration was longer and the capacity density was higher than that of the battery using the positive electrode of No. 6.
第１図は、本発明を説明するための有機溶媒電
池の１例の縦断面図、第２図は、各試料番号の正
極を用いた有機溶媒電池の放電特性を表わす。
１……正極、２……負極（リチウム円板）、３
……セパレータ、４……ケース、５……負極封口
板、６……ガスケツト。
FIG. 1 is a longitudinal sectional view of an example of an organic solvent battery for explaining the present invention, and FIG. 2 shows the discharge characteristics of an organic solvent battery using positive electrodes of each sample number. 1...Positive electrode, 2...Negative electrode (lithium disk), 3
... Separator, 4 ... Case, 5 ... Negative electrode sealing plate, 6 ... Gasket.
Claims (1)
に加熱処理された二硫化鉄を含む有機溶媒電池の
正極。1 The active material is heated to 400 to 600℃ in an inert gas atmosphere.
An organic solvent battery positive electrode containing iron disulfide that has been heat-treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56037834A JPS57152672A (en) | 1981-03-18 | 1981-03-18 | Anode of organic solvent cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56037834A JPS57152672A (en) | 1981-03-18 | 1981-03-18 | Anode of organic solvent cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57152672A JPS57152672A (en) | 1982-09-21 |
| JPH0251217B2 true JPH0251217B2 (en) | 1990-11-06 |
Family
ID=12508553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56037834A Granted JPS57152672A (en) | 1981-03-18 | 1981-03-18 | Anode of organic solvent cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57152672A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100261054A1 (en) * | 2009-04-14 | 2010-10-14 | Michael Pozin | Lithium Primary Cells |
-
1981
- 1981-03-18 JP JP56037834A patent/JPS57152672A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57152672A (en) | 1982-09-21 |
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